CN105367559A - Epoxy resin based on uracil and preparation method and application thereof - Google Patents
Epoxy resin based on uracil and preparation method and application thereof Download PDFInfo
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- CN105367559A CN105367559A CN201410417818.3A CN201410417818A CN105367559A CN 105367559 A CN105367559 A CN 105367559A CN 201410417818 A CN201410417818 A CN 201410417818A CN 105367559 A CN105367559 A CN 105367559A
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Abstract
The invention discloses a kind of epoxy resin and its preparation method and application based on uracil. The epoxy resin has chemical structure shown in following formula:
It has good mechanical property and thermal property after cured, can be widely applied in adhesive, coating or other composite materials with very high epoxide number; The preparation method includes: after mixing uracil, epoxy halogenopropane with catalyst, in 90~110 DEG C of 0.5~2h of reaction, then 20~40 DEG C are cooled to, alkali compounds and water is added, the reaction was continued 2~5h, wash, go solvent, it is dry after obtain target product, the preparation process is simple, controllability is good, is easy to industrializing implementation.
Description
Technical field
The present invention relates to a kind of epoxy resin and preparation method thereof and application, particularly a kind of epoxy resin based on uridylic and its preparation method and application, belongs to material science.
Background technology
Just at present, the research of bio-based macromolecular material is mainly limited to starch plastic, Mierocrystalline cellulose, polycaprolactone (PCL), poly(lactic acid) (PLA), poly butylene succinate (PBS), polyhydroxyalkanoate (PHA), some natural polymers or the thermoplastic materials such as polyvinyl alcohol (PVA), the research for thermoset bio-based plastics is then in the starting stage.Thermosetting resin plays irreplaceable vital role because it has good dimensional stability, good thermotolerance and good processibility etc. in all respects of national economy, is a class wide application, macromolecular material that consumption is large.With renewable plant resources for raw material, research and develop novel bio-based thermosetting epoxy resin and be used for alternative existing petroleum-based products, be no matter the development trend from domestic and international bio-based plastics, or from the present Research of bio-based plastics, all seem significant and have a extensive future.
Nowadays different kind organism based platform compound is all puted forth effort in research and development, current report mainly contain furandicarboxylic acid, Isosorbide, methylene-succinic acid etc., they can be obtained through fermentation or chemical process by biological raw material, have the potentiality of the existing petroleum based material of Some substitute.But due to the restriction of chemical structure itself, the existence such as selling at exorbitant prices all in various degree of thermosetting resin prepared by these platform chemicals, performance are difficult to meet the problems such as actual requirement, constantly explore and find new bio-based platform chemicals and seem significant.
Summary of the invention
In view of the deficiencies in the prior art, an object of the present invention is to provide a kind of epoxy resin based on uridylic, and this epoxy resin has nitrogen heterocyclic, will have higher segment rigidity, thus possess good mechanical property and thermal property after solidification.
Two of object of the present invention is that providing a kind of prepares the described method based on the epoxy resin of uridylic, and this preparation technology is simple, workable, process control is good, is easy to industrializing implementation.
Three of object of the present invention is that providing described is preparing the application in curable materials system or solidify material based on the epoxy resin of uridylic.
For realizing aforementioned invention object, the technical solution used in the present invention comprises:
Based on an epoxy resin for uridylic, there is chemical structure as follows:
Further, the described epoxy resin based on uridylic is at room temperature colourless transparent liquid.
Further, the oxirane value of the described epoxy resin based on uridylic is 0.90 ~ 0.95 epoxy equivalent (weight)/100 gram resins.
A kind of preparation method of the epoxy resin based on uridylic, comprise: get 100 weight part uridylics, 250 ~ 600 parts by weight epoxy halogenopropanes and 10 ~ 30 parts of water and catalyst mix, after 80 DEG C ~ 110 DEG C reaction 0.5 ~ 3h, be cooled to 20 DEG C ~ 40 DEG C, in the hybrid reaction system after cooling, add basic cpd and water again continue reaction 2h ~ 5h at 20 DEG C ~ 40 DEG C, by obtained reaction mixture washing, except after desolventizing, drying, obtain the described epoxy resin based on uridylic.
In order to preparation method of the present invention reaches better invention effect, also can further adopt following preferred version:
Such as, described epoxy halogenopropane can be selected from but be not limited in epoxy chloropropane, epoxy bromopropane one or both.Epoxy halogenopropane replaces by different reactions from the hydroxyl of three on uridylic and a carboxyl.
Such as, described catalyzer can be selected from but be not limited in tetramethyl ammonium chloride, cetyl trimethylammonium bromide, Cetyltrimethylammonium bromide, six methyne four ammoniums one or more.Particularly preferred, the consumption of described catalyzer is 1 ~ 20 weight part.
Such as, described basic cpd can mainly select inorganic strong alkali compound, such as, its can be selected from but be not limited in magnesium hydroxide, lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, hydrated barta one or more.Particularly preferred, the consumption of the described basic cpd and water that add the hybrid reaction system after described cooling is respectively 18 ~ 100 weight parts and 60 ~ 120 weight parts.Wherein, the water adopted more preferably adopts distilled water.
Further, in the preparation process in accordance with the present invention, adding basic cpd and water, and after reacting completely, carrying out again after obtained reaction mixture can being down to room temperature washing, removing the aftertreatment such as solvent and drying.Wherein, washing can adopt deionization repeatedly to wash, such as, each use 150 weight part ~ 200 parts by weight of deionized water carries out washing 3 ~ 4 times, remove solvent and can adopt the modes such as Rotary Evaporators desolventizing, drying can adopt the modes such as vacuum-drying, but is all not limited thereto.
The described epoxy resin based on uridylic can be applicable to prepare matrix material, epoxy adhesive and coating, particularly can be applicable to prepare curable materials system or solidify material.
Such as, the described epoxy resin based on uridylic and HHPA etc. can be formed cured article, this cured article has excellent mechanical property and higher decomposition temperature, can be applied to matrix material.
As a kind of typically used mode wherein, the invention provides a kind of curable materials system, it comprises:
Basic components, comprises the epoxy resin based on uridylic of 100 weight parts and the HHPA of 20 ~ 80 weight parts; And,
Selectable components, comprises the imidazoles of 0.2 ~ 0.6 weight part.
Wherein " selectable components " is the component can selecting to add or do not add.
As another kind of typically used mode wherein, present invention also offers a kind of preparation method of solidify material, comprising:
According to the chemical constitution of described curable materials system, using based on the epoxy resin based on uridylic of component and HHPA and after the imidazoles mixing of selectable components, after 80 DEG C of solidification 1.5 ~ 2.5h, 120 ~ 160 DEG C of solidifications, 1.5 ~ 2.5h or 170 DEG C ~ 190 DEG C solidification 1.5 ~ 2.5h, obtain described solidify material, the flexural strength of described solidify material is 62-75MPa, modulus in flexure is 3100-3400MPa, when thermal weight loss quality 5%, corresponding heat decomposition temperature is 334-340 DEG C.
Compared with prior art, advantage of the present invention comprises:
(1) of the present invention based in the epoxy resin of uridylic, containing a nitrogen heterocyclic in uridylic, compare phenyl ring and have larger polarity, moving freely of polymer segment can be hindered, thus make described have higher thermotolerance and mechanical strength based on after the epoxy resin cure of uridylic, can widespread use in sizing agent, coating or other matrix material;
(2) preparation technology of the epoxy resin based on uridylic of the present invention is simple, workable, process control is good, is easy to industrializing implementation.
Accompanying drawing explanation
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, be briefly described to the accompanying drawing used required in embodiment or description of the prior art below, apparently, the accompanying drawing that the following describes is only some embodiments recorded in the present invention, for those of ordinary skill in the art, under the prerequisite not paying creative work, other accompanying drawing can also be obtained according to these accompanying drawings.
Fig. 1 is the hydrogen nuclear magnetic resonance spectrogram of the epoxy resin based on uridylic of preparation in embodiment 1.
Embodiment
For making the object, technical solutions and advantages of the present invention clearly, below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in detail.The example of these preferred implementations illustrates in the accompanying drawings.Shown in accompanying drawing and the embodiments of the present invention described with reference to the accompanying drawings be only exemplary, and the present invention is not limited to these embodiments.
At this, also it should be noted that, in order to avoid the present invention fuzzy because of unnecessary details, illustrate only in the accompanying drawings with according to the closely-related structure of the solution of the present invention and/or treatment step, and eliminate other details little with relation of the present invention.
Embodiment 1
By 112 grams of uridylics and 1116 grams of epoxy chloropropane mixing, temperature rises to 85 DEG C, adds tetramethyl ammonium chloride 5 grams, and be cooled to 30 DEG C after reaction 1.5h, then drip containing 300 grams, 30wt% sodium hydroxide, 1h drips off, and continues reaction 3h.After question response system is down to room temperature, use 200mL deionized water wash, wash 4 times altogether, then use Rotary Evaporators desolventizing, 50 DEG C of vacuum-drying 12h, obtain pale yellow transparent thick liquid, and namely based on the epoxy resin 210 grams of uridylic, productive rate is 94.5% at every turn.
The epoxy resin based on uridylic of above-mentioned gained is carried out Structural Identification, and infrared spectrogram as shown in Figure 1.Qualification result is: in infrared spectrogram, have 3050cm
-1, 2960cm
-1, 2930cm
-1, 2850cm
-1, 1698cm
-1, 1648cm
-1, 1460cm
-1, 1380cm
-1, 1250cm
-1, 820cm
-1deng charateristic avsorption band; ?
1h nucleus magnetic resonance (CD
3cl is solvent) in have 7.2ppm, 5.8ppm, 4.5ppm, 4.0ppm, 3.1ppm, 3.0 ~ 2.6ppm, characteristic chemical shifts oxirane value be 0.95 epoxy equivalent (weight)/100 gram resins.The epoxy resin based on uridylic of gained has following structure:
The HHPA of the epoxy resin based on uridylic of 100 obtained weight parts and 120 weight parts is mixed, add the imidazoles of 0.5 weight part, then respectively at 80 DEG C of solidification 2h, after 130 DEG C of solidifications 2h and 160 DEG C of solidification 2h, obtain containing the cured article based on the epoxy resin of uridylic, the modulus in flexure of this cured article is 3400MPa, and flexural strength is 75MPa, when thermal weight loss quality is 5%, corresponding decomposition temperature is at 340 DEG C.
Embodiment 2
By 112 grams of uridylics and 700 grams of epoxy bromopropane mixing, temperature rises to 110 DEG C, adds Cetyltrimethylammonium bromide 20 grams, and be cooled to 30 DEG C after reaction 0.5h, then drip 35% potassium hydroxide solution 300 grams, 1h drips off, and 30 DEG C are continued reaction 3h.After question response system is down to room temperature, then use 200mL deionized water wash at every turn, wash 4 times altogether, then use Rotary Evaporators desolventizing, 50 DEG C of vacuum-drying 12h, must based on the epoxy resin 217 grams of uridylic, productive rate is 97.5%.
The epoxy resin based on uridylic of above-mentioned gained is carried out Structural Identification, and qualification result is substantially identical with embodiment 1.Oxirane value is 0.91 epoxy equivalent (weight)/100 gram resins after measured.By the epoxy resin based on uridylic of 100 weight parts and the mixing of 55 weight part HHPAs, add the imidazoles of 0.5 weight part.Then respectively at 80 DEG C of solidification 2h, after 130 DEG C of solidifications 2h and 160 DEG C of solidification 2h, obtain containing the cured article based on the epoxy resin of uridylic.The modulus in flexure contained based on the cured article of the epoxy resin of uridylic of gained is 3100MPa, and flexural strength is 63MPa, and when thermal weight loss quality is 5%, corresponding decomposition temperature is at 334 DEG C.
Embodiment 3
By 112 grams of uridylics, 800 grams of epoxy chloropropane mixing, temperature rises to 90 DEG C, adds six methyne four ammonium 12 grams, and after 60 DEG C of reaction 1h, be cooled to 30 DEG C, then drip and then drip 35% potassium hydroxide solution 300 grams, 1h drips off, and 30 DEG C are continued reaction 3h.After question response system is down to room temperature, then use 200mL deionized water wash at every turn, wash 4 times altogether, then use Rotary Evaporators desolventizing, 50 DEG C of vacuum-drying 12h, must based on the epoxy resin 210 grams of uridylic.
Identified by the epoxy resin based on uridylic of above-mentioned gained, qualification result is substantially identical with embodiment 1.Oxirane value is 0.92 epoxy equivalent (weight)/100 gram resins after measured.100 weight parts based on the epoxy resin of uridylic and the mixing of 41 weight part HHPAs, should be added the imidazoles of 0.5 weight part.Then respectively at 80 DEG C of solidification 2h, after 130 DEG C of solidifications 2h and 160 DEG C of solidification 2h, obtain containing the cured article based on the epoxy resin of uridylic.The modulus in flexure contained based on the cured article of the epoxy resin of uridylic of gained is 3200MPa, and flexural strength is 64MPa, and when thermal weight loss quality is 5%, corresponding decomposition temperature is at 335 DEG C.
Embodiment 4
By 112 grams of uridylics and 700 grams of epoxy chloropropane mixing, temperature rises to 100 DEG C, adds cetyl trimethylammonium bromide 18 grams, 35 DEG C are cooled to after reaction 1h, then add 28 grams of calcium hydroxides and 60 grams of distilled water, forming reactions system, continue reaction 3h at 35 DEG C.After question response system is down to room temperature, filtering solids residue, then use 200mL deionized water wash at every turn, and wash 4 times altogether, then use Rotary Evaporators desolventizing, 50 DEG C of vacuum-drying 12h, must based on the epoxy resin 210 grams of uridylic.
The epoxy resin based on uridylic of above-mentioned gained is carried out Structural Identification, and qualification result is substantially identical with embodiment 1.Oxirane value is 0.46 epoxy equivalent (weight)/100 gram resins after measured.By 100 weight parts based on the epoxy resin of uridylic and the mixing of 55 weight part HHPAs, then respectively at 80 DEG C of solidification 2h, after 130 DEG C of solidifications 2h and 160 DEG C of solidification 2h, obtain containing the cured article based on the epoxy resin of uridylic.The modulus in flexure contained based on the cured article of the epoxy resin of uridylic of gained is 3340MPa, and flexural strength is 62MPa, and when thermal weight loss quality is 5%, corresponding decomposition temperature is at 339 DEG C.
Should be appreciated that above-described embodiment is only and technical conceive of the present invention and feature are described, its object is to person skilled in the art can be understood content of the present invention and implement according to this, can not limit the scope of the invention with this.All equivalences done according to spirit of the present invention change or modify, and all should be encompassed within protection scope of the present invention.
Claims (10)
1., based on an epoxy resin for uridylic, it is characterized in that there is chemical structure as follows:
2. the preparation method of the epoxy resin based on uridylic according to claim 1, it is characterized in that comprising: get 100 weight part uridylics, 250 ~ 600 parts by weight epoxy halogenopropanes and 10 ~ 30 parts of water and catalyst mix, after 80 DEG C ~ 110 DEG C reaction 0.5 ~ 3h, be cooled to 20 DEG C ~ 40 DEG C, in the hybrid reaction system after cooling, add basic cpd and water again continue reaction 2h ~ 5h at 20 DEG C ~ 40 DEG C, by obtained reaction mixture washing, except after desolventizing, drying, obtain the described epoxy resin based on uridylic.
3., according to claim 2 based on the preparation method of the epoxy resin of uridylic, it is characterized in that described epoxy halogenopropane comprises epoxy chloropropane and/or epoxy bromopropane.
4., according to claim 2 based on the preparation method of the epoxy resin of uridylic, it is characterized in that described catalyzer comprises any one or two or more combinations in tetramethyl ammonium chloride, cetyl trimethylammonium bromide, Cetyltrimethylammonium bromide, six methyne four ammoniums.
5. according to claim 2 or 4 based on the preparation method of the epoxy resin of uridylic, it is characterized in that the consumption of described catalyzer is 0.1 ~ 20 weight part.
6. the preparation method of the epoxy resin based on uridylic according to claim 2, is characterized in that described basic cpd comprises any one or two or more combinations in magnesium hydroxide, lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, hydrated barta.
7. according to any one of claim 1-6 based on the epoxy resin of uridylic in the application preparing curable materials system or solidify material.
8. a curable materials system, is characterized in that comprising:
Basic components, based on the epoxy resin of uridylic and the HHPA of 20 ~ 80 weight parts according to any one of the claim 1-6 comprising 100 weight parts; And,
Selectable components, comprises the imidazoles of 0.2 ~ 0.6 weight part.
9. a preparation method for solidify material, is characterized in that comprising:
According to the chemical constitution of curable materials system described in claim 8, using based on the epoxy resin based on uridylic of component and HHPA and after the imidazoles mixing of selectable components, after 80 DEG C of solidification 1.5 ~ 2.5h, 120 ~ 160 DEG C of solidifications, 1.5 ~ 2.5h or 170 DEG C ~ 190 DEG C solidification 1.5 ~ 2.5h, obtain described solidify material.
10. the preparation method of solidify material according to claim 9, it is characterized in that the flexural strength of described solidify material is 62-75MPa, modulus in flexure is 3100-3400MPa, and when thermal weight loss quality 5%, corresponding heat decomposition temperature is 334-340 DEG C.
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Citations (7)
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2014
- 2014-08-22 CN CN201410417818.3A patent/CN105367559A/en active Pending
Patent Citations (7)
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| US3503979A (en) * | 1968-01-17 | 1970-03-31 | Ciba Ltd | Heterocyclic n,n'-diglycidyl compounds |
| US3793248A (en) * | 1968-04-17 | 1974-02-19 | Ciba Geigy Ag | Adducts,containing epoxide groups,from polyepoxide compounds and binuclear n-heterocyclic compounds |
| CH510690A (en) * | 1969-07-10 | 1971-07-31 | Ciba Geigy Ag | Heterocyclic diglycidyl cpds prepd from barbituric aicd - derivs and methylhalohydrins-ns |
| US4117029A (en) * | 1973-10-11 | 1978-09-26 | Nitto Kasei Co. Ltd. | Halogen-containing resin composition containing organic substance as stabilizer |
| US4459392A (en) * | 1983-02-25 | 1984-07-10 | Unitika Limited | Method of making and polymer of heat resistant polyester using diglycidilhydantoins, diglycidiluracils, diglycidilbarbituric and isocyanuric acids |
| CN1361800A (en) * | 1999-07-28 | 2002-07-31 | 拜尔公司 | Solvent-free, room temperature curing reactive systems and the use thereof in the production of adhesives, sealing agents, casting compounds, molded articles or coatings |
| CN1513914A (en) * | 2002-12-27 | 2004-07-21 | ������������ʽ���� | Polyphenyl thioether resin composition |
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Application publication date: 20160302 |